Graft copolymers of unsaturated polyethers on polyamide and polyester substrates

ABSTRACT

Dye receptive polymers may be prepared by grafting polyethers containing ethylenic unsaturation onto a fiber forming polyamide backbone. The graft copolymer is prepared by passing a polymer whose surface is coated with the vinyl monomer through a zone of irradiation.

United States Patent Magat et al.

[ 1 June 13, 1972 [54] GRAFT COPOLYMERS OF UNSATURATED POLYETHERS ON POLYAMIDE AND POLYESTER SUBSTRATES [72] Inventors: Eugene Edward Magat; David Tanner, both of Wilmington, Del.

[60] Continuation of Ser. No. 863,047, Dec. 30, 1959, abandoned, Continuation-in-part of Ser. Nos. 499,754, April 6, 1955, abandoned, and Ser. No. 503,790, April 25, 1955, abandoned, which is a division of Ser. No. 735,288, May 14, 1958, Pat. No. 3,188,228.

[52] US. Cl. "260/857 G, l l7/93.3l, 204/159. 15, 204/ 1 59. 16, 204/159. 1 7, 204/159. 1 9, 260/860,

[51] Int. Cl. ..C08g 41/04 [58] Field ofSearch ..260/857, 860, 873; 204/l54.l5

[56] References Cited UNITED STATES PATENTS 2,921,006 l/l960 Schmitz ..204/l54.l5

Primary Examiner-Paul Lieberman Anorneyl. R. McGrath ABSTRACT Dye receptive polymers may be prepared by grafting polyethers containing ethylenic unsaturation onto a fiber forming polyarnide backbone. The graft copolymer is prepared by passing a polymer whose surface is coated with the vinyl monomer through a zone of irradiation.

12 Claims, 4 Drawing Figures PATENTEDJun 1 3 m2 3. 670 O48 sum 10$ 2 Fig.1

INVENTORS EUGENE EDWARD MAGAT DAVID TANNER ATTORNEY wage; SHIP sum 2 BF 2 PATENTEDJUN 13 IS GRAFT COPOLYMERS OF UNSATURATED POLYETHERS N POLYAMIDE AND POLYESTER SUBSTRATES This application is a continuation of application Ser. No. 863,047 filed Dec. 30, 1959, now abandoned. This application is a continuation in part of US. application Ser. No. 499,754, filed Apr. 6, 1955, now abandoned, and application Ser. No. 503,790, filed Apr. 25, 1955, now abandoned, and a division of U.S. application Ser. No. 735,288, filed May 14, 1958, now US. Pat. No. 3,188,228.

This invention relates to product and process. More particularly it concerns a process for chemically adhering an organic compound to a shaped article produced from a synthetic organic condensation polymer and the graft copolymer product formed thereby.

OBJECTS It is an object of the present invention to provide a process for chemically adhering an organic compound to a shaped article produced from a synthetic organic condensation polymer.

Another object is to provide a novel shaped article comprising a solid synthetic organic condensation polymer to which an organic compound is grafted.

Another object is to provide shaped articles of a solid synthetic organic condensation polymer having new and desirable properties obtained by grafting an organic compound to the said shaped article without substantial sacrifice of those properties inherent in the unmodified condensation polymer. The modified polymer is thus known as a graft copolymer. Thus, as an example, in accordance with this invention a textile formed from a condensation polymer may be provided which is freer from static, more dyeable, more resistant to soiling, more resilient or crease resistant, and shows better adhesion to elastomers, and the like, than textiles heretofore obtainable from the said condensation polymer.

It is a still further object of this invention to provide a process whereby a shaped article of condensation polymer such as a textile can be modified in its properties, as explained hereinabove, by applying a suitable modifier to a shaped substrate, and inducing chemical bonding therebetween.

A still further object of this invention is to provide a process for modifying a shaped condensation polymer throughout its bulk by applying a suitable vinyl monomer to the surface thereof. permitting it to penetrate throughout the substrate, and inducing grafting to said shaped condensation polymer.

Yet another object of this invention is to provide a process for modifying a shaped article of synthetic condensation polymer by grafting to it a non-polymerizable organic chemical compound.

Still another object of this invention is to provide a process for modifying a textile formed from shaped condensation polymer filaments by applying to said textile a highly fluid polymeric material or fluid polymeric solution, coating each filament uniformly and continuously, and inducing chemical bonding therebetween, whereby a surface-modified filament and textile is obtained, which retains the attractive handle and aesthetic properties of the original textile.

Another object of this invention is to provide a bactericidal textile with a germicide permanently grafted thereto.

These and other objects will become apparent in the course of the following specification and claims.

STATEMENT OF THE INVENTION In accordance with the present invention a shaped article produced from a synthetic organic condensation polymer, in intimate contact with an organic compound, is subjected to bombardment by ionizing radiation to produce chemical bonds between the shaped article and the organic compound. In one embodiment, an organic modifier is applied to the surface of a shaped article produced from a synthetic organic condensation polymer and the shaped article is thereafter irradiated with ionizing radiation to induce chemical bonding.

LII

For deep seated modification the organic compound is permitted to diffuse into the substrate prior to the irradiation. Alternatively, the organic modifier, especially when it is of high molecular weight, may remain upon the surface of the polymer substrate during the irradiation step, thus producing a uniform coating chemically grafted to the polymer substrate. The organic compound employed as modifier may be a nonpolymerizable organic compound or it may be polymerizable; either form is chemically grafted to the shaped article formed from an organic condensation polymer.

DEFINITIONS By the term synthetic organic condensation polymer" is meant a polymer which can be formed by polymerization with elimination of small molecules such as HCl H O, NaCl NH,, and the like. These polymers are also characterized by their ability to hydrolyze to a monomer. Another characteristic which distinguishes condensation polymers (for instance, from addition polymers) is that the repeating units which form an integral part of the polymer chain are linked by other than carbon-to-carb0n bonds. Among such polymers may be mentioned polyamides, polyureas, polyurethanes, polyesters, polyoxymethylenes, polyethers (epoxy polymers), polyacetals, polysulfonamides, and the like, and copolymers of such materials. These polymers are comprehensively discussed by Flory in Principles of Polymer Chemistry," Cornell University Press, lthaca, N.Y. (1953), pp. 37-50. The preferred condensation polymers are those which are substantially linear, i.e., those which are produced from predominantly difunctional reactants. By substantially linear is meant that minor amounts of cross-linking may be present (prior to irradiation), provided the polymer exhibits the general solubility and melting characteristics of a linear, as distinguished from a highly cross-linked polymer.

By graft copolymer is meant a polymer which is modified, after polymerizing and shaping, by chemically bonding thereto, molecules of a chemically dissimilar organic compound.

By irradiation is meant the process by which energy is propagated through space, the possibility of propagation being unconditioned by the presence of matter (as distinguished from mere mechanical agitation in a material medium such as is characteristic of energy produced by a sonic or ultrasonic transducer), although the speed, direction, and amount of energy transferred may be thus affected.

By ionizing radiation" is meant radiation with sufficient energy to remove an electron from a gas atom, forming an ion pair; this requires an energy of about 32 electron volts (ev) for each ion pair formed. This radiation has sufficient energy to non-selectively break chemical bonds; thus, in round numbers radiation with energy of 50 electron volts (ev) and above is effective for the process of this invention. The ionizing radiation of the process of this invention is generally classed in two types: high energy particle radiation, and ionizing electromagnetic radiation. The effect produced by these two types of radiation is similar, the essential requisite being that the incident particles or photons have sufficient energy to break chemical bonds and generate free radicals.

The preferred radiation for the practice of this invention is high energy ionizing radiation, and has an energy equivalent to at least 0.1 million electron volt (Mev). Higher energies are even more effective; there is no known upper limit, except that imposed by available equipment.

By an organic compound is meant a material having the formula CX where X is a member of the group consisting of hydrogen, halogen, nitrogen, nitrogen radical, oxygen, oxygen radical, sulfur, sulfur radical or organic radical. By organic radical is meant a radical predominantly hydrocarbon except for the presence of substituents immediately hereinbefore listed. Where one or more of the X5 is organic radical, it is preferred that it be linked to the CX residue by a carbon-tocarbon bond. Furthermore, the C may be doubly bonded to no more than one S=r O=atom; i.e., only one pair of Xs may be replaced by a divalent oxygen or sulfur atom. Typical compounds included are hydrocarbons, alcohols, acids, ethers, ketones, esters, aldehydes, isocyanates, sulfonates, mercaptans, thioethers, disulfides, nitriles, nitro compounds, amines, amides, and halides. Compounds with ethylenic unsaturation are especially preferred, since a minimum radiation dose is required to graft a given weight of modifier. However, nonpolymerizable organic compounds (free from aliphatic unsaturation) are also readily grafted, to produce efiective modification of polymer properties. Of these compounds, the chain transfer agents are preferred.

Another useful class of modifiers is the high molecular weight compounds, especially polymers. These compounds are readily and effectively grafted since a single site of attachment bonds a relatively large weight of modifier, due to the large molecular weight. The large molecule tends to prevent penetration by these modifiers, and hence they are especially useful in creating surface effects. The polymeric modifiers especially preferred for textile uses are those which may be applied to the textile as a low viscosity solution or melt, thus ensuring that each filament is completely coated.

DRAWINGS FIG. 1 is a target arrangement for sample bombardment with proton, deuteron, and alpha particles. in the illustration the particle is accelerated in cyclotron l and following emergent particle path 2 passes through window and beam defocusing arm 3 wherein the beam is spread. Thereafter the spread beam is passed through carbon shutter impinging on sample 5, the said sample being enclosed in wrapper 6. Electrometer 7 measures the beam-out current at the carbon shutter.

H0. 2 shows a section of the defocused beam pattern. The rectangular checker area 8 represents the irradiated area of sample with curves 9 and 10 denoting intensity distribution along the x and y coordinates of the sample, respectively.

FIG. 3 is a typical target arrangement for fast neutron bombardment. Beryllium target 1 1 is bombarded with 24 mev deuterons generated in cyclotron l. The neutrons produced are impinged on target 12 disposed along the emergent neutron beam 13.

FIG. 4 is a flow sheet illustrating a typical embodiment wherein the process of the present invention is applied to a yarn tow which after impregnation with modifier, radiation, a wash; a drying operation and cutting is available as modified staple for yarn production.

EXPERIMENTAL PROCEDURES AND UNITS Compositions are given in parts by weight or weight per cent, unless otherwise noted.

Radiation dosages are given in units of Mrad" (millions of rads), a rad" being the amount of high energy radiation of any type which results in an energy absorption of 100 ergs per gram of water or equivalent absorbing material. Alternatively, dosages may be indicated in terms of exposure in watt seconds per square centimeter of substrate treated.

Unless otherwise noted, 66 nylon fabric employed in the examples is a taffeta fabric, woven from 70 denier polyhexamethylene adipamide continuous filament yarn having a denier per filament of 2.0. The polyamide is produced from hexamethylenediamine and adipic acid (ergo 66) and has a relative viscosity (as defined in U.S. Pat. No. 2,385,890) of 37, 39 equivalents of NH ends and 92 equivalent of C00l-l ends per 10 grams of polymer (referred to hereinafter as 39 amine ends and 92 carboxyl ends, respectively). The polymer is prepared using 0.34 mol per cent acetic acid stabilizer (which ends are, of course, not titratable), which is equivalent to 15 amine ends. From these data, following the method of G. B. Taylor and J. E. Waltz (Analytical Chemistry," Vol. 19, p. 448: 1942) the molecular weight (number average) is calculated to be about 13,700.

This analytical method is useful not only for determining end groups present in unmodified polymer, but it may be used also to determine the number of active acidic or amine end groups attached to polyamides by the grafting reaction. However, since the above method requires solution of the polymer sample in hot benzyl alcohol, and some of the polymers of this invention are not completely soluble in this solvent, other procedures are useful. For example, satisfactory results are obtained by gently boiling a 0.33 gram sample of polymer in 10 ml. aqueous 0.1 N NaOl-l, followed by backtitrating the excess base with 0.1 N HCl using bromo-cresol green indicator.

The standard washing to which samples are subjected consists of a 30-minute immersion in 18 liters of 70 C. water contained in a 20-liter agitation washer. The wash solution contains 0.5 percent of detergent. The detergent employed is that sold under the trademark Tide of Proctor and Gamble Company of Cincinnati, 0. This detergent contains, in addition to the active ingredient, well over 50 percent (sodium) phosphates (Chemical Industries, 60, 942, July 194-7)v Analysis shows the composition to be substantially as follows:

The static propensity of the fabric is indicated in terms of direct current resistance in ohms per square, measured parallel to the fabric surface, at 78 F. in a 50 percent relative humidity atmosphere. High values, reported as the logarithm (to the base 10) of the resistivity (log R) indicate a tendency to acquire and retain a static charge. It should be noted that highly hydrophobic unmodified polymer substrates have such a high resistivity that the log R determined may depend somewhat on the sensitivity of the meter employed; log R values of 13 to over 15 have been observed, using the same fabric and different meters. However, these differences substantially disappear when a satisfactory antistatic modification is produced, e.g., for log R values of l 1 or less. Moreover, data reported in any given example are consistent, i.e., all measurements were made on the same instruments under the same conditions. A meter suitable for this determination is described by l-layek and Chromey, American Dyestuff Reporter, 40, 225 1951).

Wickability as measured in the examples is determined by placing a drop of water upon the fabric, and measuring the diameter of the wet spot after a standard time interval, e.g., 60 seconds. Alternatively, especially useful where decreased wickability is obtained, is a determination of the length of time required for a drop placed upon the fabric to disappear by soaking into the fabric. Discrepancies observed between control fabrics in the different examples are thought to be due to different preparation techniques. Data within each example are comparable.

Where quantitative values for hole melting are presented, they are measured by dropping heated glass beads of constant weight and diameter from a fixed height from a constant temperature oven onto the fabric. The temperature at which the fabric is stained is called the first damage temperature, and the temperature at which the glass bead melts completely through the fabric is referred to as hole-melting temperature. Where the hole-melting tendency is presented in qualitative terms, the designation poor" (referring to polyamides) denotes a quantitative rating of about 300 C.; fair a rating of about 400 C. to about 500 C.; good a rating of about 600 C. or slightly better; and excellent a rating well over 600 C.

The fiber melt temperature reported in some examples is determined by placing a thread, unraveled from a fabric if necessary, upon an electrically heated tube and observing the tube temperature at which visible melting, fusing of filaments to the tube, or instantaneous decomposition occurs.

Post-formability is evaluated by contacting a sample yarn with a tube heated to about 225 C. A fiber which can be drawn in contact with the tube and without substantially fusing the filaments, to two or three times its original length is designated e1astic." When the stretch is retained without restraint after cooling, it is designated post-formable.

Crease recovery is evaluated by crumpling a fabric in the hand, and observing the rate at which it recovers from this treatment. Wet crease recovery indicates the rate and extent of disappearance of creases from the crumpled fabric when it is wetted. Numerical values are obtained using the Monsanto Crease Recovery Method, described as the vertical strip crease recovery test" in the American Society for Testing Materials Manual, Test No. D1295-53T. In determining wet crease recovery by this method, the specimens are soaked for at least 16 hours in distilled water containing 0.5 percent by weight of Tween 20, a polyoxyalkylene derivative of sorbitan monolaurate, a wem'ng agent marketed by the ATLAS Powder Company, Wilmington, Dela. Immediately prior to testing, excess water is removed from the test fabrics by blotting between layers of a paper towel. Results are reported as per cent recovery from a standard crease in 300 seconds.

The following examples are cited to illustrate the invention. They are not intended to limit it in any manner.

EXAMPLE 1 A sample of 66" nylon fabric is soaked in liquid methoxydecaethyleneoxy methacrylate. After removal of excess liquid by wringing, but while still wet, it is enclosed in an aluminum foil wrapper and subjected to electron irradiation in a l Mev resonant transformer with a beam-out current of 560 microamperes. The sample is placed on a conveyor belt which carries it through the electron beam at a rate of 16 inches per minute. At the sample location, the beam supplies an irradiation dose, for textile samples, of 5.6 X rad (5.6 Mrad) per pass. The sample is traversed back and forth across the beam until a total dose of 17 Mrad is attained. The sample is given the standard wash, rinsed in distilled water and dried. Its direct current resistance in ohms is then measured. Its logarithm is 9.8. After five washings, the value rises only to 10.7. After ten additional washings, the value increases only to 10.9. This compares favorably with cotton (a material with but little tendency to accumulate static charges) which has a value of 10.8. The product has a softening point of 239 C., and except for a trace, is soluble in 98 percent formic acid. A control sample of the original fabric has a log resistivity of 13.2, a softening point of 247 C., and is completely soluble in formic acid. When exposure of the soaked, wrapped sample to irradiation is increased to 67 Mrad, although the product displays good antistatic properties (a log resistivity of 10.7), it is insoluble in 98 percent formic acid and is infusible, indicating a high degree of cross-linking.

EXAMPLE 2 In order to test the penetration of electron radiation into relatively thick samples, 60 samples of polyhexamethylene adipamide fabric are individually padded with liquid methoxydecaethyleneoxy methacrylate and thereafter stacked into a flat package of a thickness equal to the sum of the thicknesses of the 60 pieces, a total of about 0.24 inch. The package is wrapped in aluminum foil and is irradiated from one side only in the equipment and under the conditions of Example 1 to a total irradiation dose of 33 Mrad. The samples, numbered from 1 to 60, beginning at the top (nearest the electron source) are then subjected to a series of various treatments during which the log resistivity of selected samples, after being rinsed and dried, is measured and is reported in Table l. The first treatment is a series of consecutive standard washings. Column A is the observation taken after the second washing, while column B is taken after the 15th. The 15 consecutive washings are followed by a sodium chlorite bleach and another standard washing, the subsequent observation being shown in column C. The samples are then washed 14 hours in synthetic detergent. Column D reports the log resistivity observed. Finally the samples are given 5 consecutive washings in hot soapy water, these final values being shown in column These results show that the electron beam penetrates the fabric pile far enough to induce appreciable modification in about the top 30 fabric layers. The total thickness effectively penetrated by the l Mev electrons is about 0.1 inch (0.25 cm.).

EXAMPLE 3 A series of nylon tafieta fabrics are scoured in a solution containing 0.5 percent olive oil soap flakes and 0.46 percent trisodium phosphate. The scoured fabrics are soaked 8 hours in an aqueous solution containing 25 percent acrylic acid. Excess liquid is removed from the samples, and they are packaged in 5 mil polyethylene film packets and are then irradiated. The radiations used in this example are produced in a cyclotron, arranged to bombard the samples with high speed protons, deuterons, alpha particles, or neutrons. Duplicate samples for each test are provided. The arrangement of the samples with respect to the cyclotron, for charged particle irradiation is shown in FIG. 1. In this example a distance from window to carbon shutter of 24 inches and from carbon shutter to sample of 5 inches is used, the beam width at the sample being 7 cm. FIG. 2 shows schematically the distribution of the charged particles as they impinge upon the fabric samples. Ionized hydrogen molecules (H are accelerated in the cyclotron, but are dissociated to form a proton (H beam on pasing through the carbon shutter. Fast neutrons are produced by bombarding a beryllium target with 24 Mev deuterons. The emergent beam from the beryllium target impinges upon the sample at a distance of 30 inches from the target, arranged as shown in FIG. 3. These neutrons at this position have an average energy of 10 Mev.

After irradiation, the ungrafied acrylic and polyacrylic acid is removed by rinsing the fabrics in distilled water, boiling them for 1 hour in a 5 percent aqueous solution of sodium carbonate, rinsing again in distilled water, followed by boiling in a 2 percent aqueous solution of acetic acid followed by a second distilled water rinse. The solution-to-fabric weight ratio is 500:1 in each operation. The exposure conditions and the results of the tests given to each sample are indicated in Table 2. Prior to testing, duplicate swatches to samples 3A, 3B, 3C, and 3D are dyed with a basic dye as shown in Example 16. The location of the irradiated portion is clearly seen because it is deeply dyed by the basic dye, due to the grafted polyacrylic acid. Fabric tests subsequently made on duplicate samples 3A to 3D are carried out on the areas corresponding to those which were deeply dyed.

The weight gain due to acrylic acid grafied to each sample is indicated in Table 2, as well as the total of original carboxyl groups plus those attached to the nylon via grafting, as determined by titration as explained hereinabove. Carboxyl group concentration found in a typical control nylon sample (3E) is shown for comparison. Following the carboxyl group determination, a portion of each sample is boiled for 1 hour in maleic acid, a weight gain of 5 percent is observed. When a percent aqueous sodium carbonate, forming the sodium salt of portion of the fabric is dyed with a basic dye, the dyed crossthe grafted acrylic acid. The log R values are indi ated in section shows that the maleic acid has penetrated the fiber, Table 2. In addition, the wickability of the sodium salt of the n i grafted hr gh its in ri r en h m l i acidgrafted acrylic acid modification is determined; its resistance 5 grafted y n is convened to the Calcium Salt by boiling in l to hole melting is estimated by dropping hot ashes f a percent calcium acetate solution, the resulting fabric is found burning cigarette upon the fabri to have excellent resistance to hole melting.

TABLE 2.IRRA1)IATON CONDITIONS AND PROPERTIES OF THE MODIFIED SAMPLES Sample Number 3A 3B 3C 3D 3E Particles 12 Mev Ht 48 Mev He. 24 Mev D+. l0 Mev neutrons Current (my amp) 80 40 Total beam exposure 1 amp-hr Integrated current flux amp sec m?) Accumulated exposure ([1 a-hrs.)

(ontroL Dosage mrad 1 l Percent weight gain of the sample exposed to the beam H 13.9 17 14.5 3.5 l s 0. COOH/IO g 1,900. 2,350.. 1,950 500. 90. Log R 7.5 r 7.5."- 7.5 10.1-.. 13.3. Wlckability ol' the sodium salt, (time in sec. for the disappearance 3 sec 3 Sec 3 see 60 sec.

of a drop of water). Hoe-melting resistance Very good... Very good Very good Half-way between control Very poor.

and samples 3A, 3B, 3C.

l-I+=proton.

lI, =a particles.

D =deuteroin EXAMPLE 4 EXAMPLE 6 A sample coded 6A of 66 nylon fabric is immersed in liquid acrylonitrile. It is then wrapped in aluminum foil and ir- A sample of 66" nylon fabric is immersed in liquid acrylonitrile. It is then wrapped in aluminum foil and irradiated with 2 Mev X-rays, as described below, until a dose of a e in e appar us and un er the conditions of Example 23 Mrad is attained. 1 until a dose of 17 Mrad is attained. The product softens at The sample is exposed to X-radiation using a resonant trans- 240 C. and is almost completely soluble in formic acid. It is former X-ruy machine marketed by the General Electric Comobserved to possess a higher crease resistance and greater un Schenectady NY, k n as a T Milli V l M resiliency than the original sample. This improved resiliency is bile X-ray Unit." This machine is described by E. E. Charlton retained even after 15 standard washings following a washing and W. F. Westendorf in the Proceedings of the First National in dimelhylformamide iasolvem Polyacrylonmfley Electronics Conference, p. 425, October 1944. The packaged The test is repeated with nylon Samples 6C and 61), which p e is placed in an open top box m d f 1 6 i aresoaked in solutions of acrylonitrile, water and methanol as sheet lead, and positioned so that the sample is 8 cm. from the mdmfited m Table 3, for 24 hours at Each pl tungsten tube target. At this location, using a tube voltage of 2 eDdOSPd a P y y g wlih excess tl n and Mev, and a tube current of 1.5 milliamperes, the irradiation llf'mduftedi a Van de Graaff generator under h condirate for the sample in question is 1.2 Mrad per hour. The beam Hons hsted below:

irradiates a circle about 3 inches in diameter; all fabric tests 40 are made on the irradiated portion. g z i i micmamps Following the irradiation, ungrafted polymer is removed by Conveyor speed, in/mim 40 washing with dimethylformarnide. After 15 standard Tide Dose per pass, Mrad l r Number of passes 2 washings, the dried nylon fabric has a superior crease recovery Total dose Mrad 2 and greater resilience than before treatment by the process of this invention.

A second sample is immersed in liquid acrylonitrile. It is then wrapped in aluminum foil and irradiated as before to a dose of 5 Mrads. After thorough rinsing, the weight gain is 12 percent. Larger irradiation doses produce larger weight gains.

It is shown that a bulk modification has been obtained by hydrolyzing the nylon-acrylonitrile graft by a 30-minute boilofi in 3 percent sodium hydroxide. The fabric, which now contains a large number of additional carboxyl groups due to trollsnot exposed to the high energy electrons hydrolysis of the nitrile groups, is then dyed with a basic dye TABLE 3 (Du Pont Brillian Green as in Example 16). Cross sections of filaments taken from these fabrics are deeply dyed throughout the modified filament, whereas only light shades are observed After a hold-up time of 2 hours, the samples are thoroughly rinsed in dimethylformamide at 70 C., followed by acetone and then water. The weight gain of each is determined and listed in Table 3. The breaking strength of representative yarn samples from each fabric is determined after 0 and 500 hours exposure to ultraviolet light in a Weatherometer. A control, 68, is included in the table for comparison purposes; the com Yarn Breaking Strength, gm. in cross sections of filaments taken from control fabrics which 50o had received the same caustic boil-off and dyeing treatment Grafting Weatherwithout irradiation. The hydrolyzed test fabric has a log R of Sample 501mm 0 9.4 vs. 13.3 for control. 63 none none 386 30 EXAMPLE 5 7 g V H 7 6C 5/22/22 10.1 393 $8 The process of this invention is readily carried out using 65 61) 25/12/22 402 100 gamma-rays, for example, derived from cobalt 60 as shown in this example. A nylon taffeta sample is soaked for 16 hours in a 15 percent aqueous solution of maleic acid and is then Solution composition ml. acrylonitrile/ml. H,O/ml. cl-non wrapped in aluminum foil while soaking wet. The foil package is wrapped around a ea-inch glass tube which in turn is inserted The grafied acrylonitrile greatly increases the light durabiliin a l%-inch glass tube. This combination is lowered into a ty of the nylon. cobalt 60 source of gamma radiation (1.3 Mev gamma-rays). EXAMPLE 7 The dose rate available from this source is 7,200 Mrads per A series of sample swatches of tropical worsted staple fabric minute. After a total dose of 27.5 Mrad, the sample is prepared from polyethylene terephthalate filaments are removed and scoured in hot water. After extracting ungrafted soaked in a 50 percent solution of acrylonitrile dissolved in a mixed solvent of 42 percent ethanol and 58 percent water, and are then heated at 90 C. for 30 minutes. The fabric samples are transferred to stainless steel pans containing 200 ml. of the treating solution, and irradiated for one pass (dose 1 Mrad) under a 2 Mev electron beam at 250 microamps. The irradiation temperature is 90 C. The grafted fabric is extracted in boiling dimethylforrnamide to remove unreacted monomer and unattached polymer, after which it is dried at 80 C. The observed weight gain is 4.4 percent. The test is repeated, with fabric samples 7A, 7B, and 7C. The composition of treating solutions, radiation dose and weight gain are shown in Table 4.

The acrylonitrile-grafted polyethylene terephthalate is found to be more resistant to alkaline hydrolysis (e.g., resistant to scouring) than the ungrafted fabric; it is also more resistant to soil pickup. Fabrics samples 7A to D, in which 7D is a control bearing no grafted acrylonitrile, are subjected to a laboratory test for laundry soiling. In this test 50 flz-inch steel balls, 0.1 g. of vacuum cleaner soil, 0.04 g. carbon black, and 20 ml. of Wagg oil* are placed in a pint Launder-Meter jar. After evaporation of the oil vehicle, 100 ml. of 0.1 percent soap solution (commercial laundry soap) is added. This mixture is then conditioned (with occasional stirring) for 1 hour at 72 C. Two 3 inch fabric swatches (test cotton control) are placed in each jar, and the mixture is tumbled for 1 hour. The swatches are then removed, rinsed thoroughly, and allowed to dry. Each swatch is then pressed for 30 seconds at 160-170C. using a hand iron. Reflectances are measured before and after washing and after pressing. At least 3 samples of each fabric are used (3jats), and the reflectances averaged. Results are recorded either Add carbon tetrachloride to make 1 liter of solution. as differential in reflectance (DR) between original sample and washed sample, or differential between original sample and ironed sample. The difference in reflectance of the samples is determined before and after the laundry test and is indicated in the column headed DR of Table 4. A low value for DR indicates nearly complete removal of soil, whereas a high value for DR indicates a fabric which retained all the applied soil. Cotton normally gives a DR value of 7 to 9, which is considered satisfactory. It is observed that soil removal improves with the amount of acrylonitrile grafted. In addition, the grafted polyethylene terephthalate fabric is more resistant to an alkaline hydrolysis. This is shown in the last column of Table 4, wherein the ratio of weight loss for the test item to that of control (7D) is indicated for a two-hour boil in 1 percent sodium hydroxide solution. Again, increased amounts of grafted acrylonitrile show increased alkaline stability. When the test is repeated using (a) a mixture of acrylonitrile and alpha-methylstyrene or (b) acrylonitrile and styrene, resistance to alkaline hydrolysis is improved over that obtained when only acrylonitrile is grafted.

A portion of sample 7C is dyed for 2 hours at the boil with a disperse dye, in a bath containing 0.13 gm/l. Celanthrene Fast Pink 38 (Cl. No.) Disp. Red 11), 1.0 g/l of an anionic hydrocarbon-sodium-sulfonate softener, 2.5 g/l dimethyl terephthalate, 2.5 g/l benzarnide. A bath-to-fabric ratio of 40:1 is employed. The dye is exhausted, and the scoured sample 7C has a deep, attractive shade. Control 7D, similarly dyed, does not exhaust the bath, and the shade is much lighter.

A second portion of 7C is dyed, using the cuprous ion technique, as follows: the sample is placed in a bath (bathtofabric ratio, 40:1) at 72 C. containing (based on weight of fabric) 1 percent Quinoline Yellow PN (C.l. No. Acid Yellow 2), 0.1 percent sodium salt of unsaturated long-chain alcohol sulfate (wetting agent); the temperature is raised to 82 C., and 2.5 percent copper sulfate is added, followed by LG percent hydroxyl ammonium sulfate; the bath is then heated to the boil for 2 hrs., followed by a scour. Test sample 7C is dyed a good shade, whereas in an attempt to similarly dye the control, 7D, it remains uncolored.

As indicated in Examples 6 and 7, highly useful products are obtained by grafting unsaturated nitriles to condensation polymer substrates. These products, in general, have improved light durability, resistance to soiling, static, and alkaline hydrolysis. Partial hydrolysis of the acrylonitrile grafted to polyethylene terephthalate results in fibers and fabrics that are more readily dyeable especially with basic dyes; the polymer substrate is also protected against hydrolytic degradation. Improvement in wickability and comfort is also noted. In addition to acrylonitrile, as shown in Examples 6 and 7, other unsaturated nitriles are useful, such as the 0:- substituted nitriles, for example, methacrylonitrile, the cyano substituted styrenes, dinitriles such as vinylidene dinitrile and the like.

Although useful modifications are obtained when as little as 1 percent acrylonitrile is grafted to the substrate, it is desirable to graft from 4 to 70 percent by weight; the preferred range is from 10 to 50 percent weight increase for polyamides.

TABLE 4 Antisoiling and Alkaline Sensitivity of Polyethylene AN=Acrylonitrile In ethanol-water solvent.

EXAMPLE 8 This example illustrates the preparation of a nylon bearing hydroxyl groups, obtained via grafting of vinyl ester, followed by hydrolysis.

Four samples of 66 nylon taffeta (coded 8A to 8D) are soaked for 20 hours in freshly distilled vinyl acetate. Each fabric sample is sealed in a polyethylene bag along with 30 ml. of vinyl acetate. Air is excluded from the package. The fabrics are irradiated using the Van de Graaf electron accelerator for the total dosage indicated in Table 5. After irradiation, the fabrics are extracted with acetone for 24 hours, using a Soxhlet extractor, followed by vacuum drying over P 0 The observed weight gains are indicated in Table 5.

The combined nylon samples having a total weight of 14 grams, are boiled for lK hours in 2 liters of 0.2 N NaOH, thus hydrolyzing the vinyl acetate. The fabrics are then thoroughly rinsed in hot distilled water and dried over P 0 The weight loss shows that the grafted polyvinyl acetate is completely hydrolyzed to give polyvinyl alcohol groups. The number of hydroxyl groups calculated from the wt. gain is indicated in Table 5.

TABLE 5 Nylon with Grafted Polyvinyl Acetate -OH groups/l gm Dose, Polyvinyl Acetate Polymer After Sample Mrad Wt. Gain, Hydrolysis 8A 2 12.9 l200 8B 3 34.7 2640 8C 4 49.9 3550 8D 5 63.0 4250 Nylon bearing grafted hydroxyl groups has a drier hand, greater liveliness and improved wickability as compared to control nylon. The log R values are about 12.0, as compared to greater than 13.3 for an unmodified nylon control.

The process is carried out employing the procedure outlines in FIG. 4. ln this embodiment, a 3 denier per filament tow of nylon is passed through a bath containing vinylacetate. After squeezing excess liquid from the tow, it is irradiated, excess homopoiymer is extracted by passing through an acetone bath, the tow being thereafter dried and cut. The speed of the tow through the process is adjusted to provide a radiation dosage of 2 Mrad. Fabric produced by weaving yarn spun from this modified staple is thereafter hydrolized. Obviously, the modified structure may be hydrolyzed at any stage, i.e., as tow as staple, as spun yarn, as fabric or the like.

A Swatch SE of polyethylene terephthalate staple fabric is immersed in 150 g of 100 percent vinyl acetate and heated at 60 C. for 30 minutes. The fabric is transferred to a 7 X ll inches stainless steel pans containing 200 ml. of the pad solution. The fabric is then irradiated at 60 C. for a total irradiation dose of 3 Mrad. The grafted fabric is extracted in boiling acetone for two hours to remove unreacted monomer and unattached polymer, after which it is dried at 80 C. A weight gain of 14 percent is noted. When the above procedure is repeated with Sample 8F, using one pass, the weight gain is 5.0 percent.

Sample BB is highly dyeable at the boil with disperse dyes, has good dye penetration and rapid dye rate in contrast to an unmodified control fabric, 86, which must be dyed with a carrier in order to obtain acceptable shades. Both 8E and BF have increased resistance to caustic hydrolysis; sample 8F shows a 60 percent lower rate of attack than control, 80.

A typical procedure for dyeing with dispersed dyes is as follows. A one gram fabric sample is boiled for 2 hours in a 40 ml. bath containing 0.02 gm. of a blue dye (l,4-diaminoanthraquinone-Na-methoxypropyl-2,3-dicarboximide, disclosed in U.S. Pat. No. 2,753,356), and 0.04 gm. ofan anionic hydrocarbon-sodium sulfonate. After dyeing, the sample is scoured for 20 minutes at 82 C. in water containing 2 percent of a condensation product of ethylene oxide and a fatty alcohol.

EXAMPLE 9 This example illustrates the direct grafting of unsaturated alcohols to condensation polymer substrates. Fabric samples are soaked for 1 hour at 95 C. in liquid modifiers, as indicated in Table 6, and are then irradiated to a dose of 10 Mrad at the soaking temperature. The samples are washed 5 times to remove excess reagents, and are then dried. In some instances, the weight gain is determined. When tested for wickability, the time required for a standard drop of water to disappear is listed in Table 6. It is noted that the grafted alcohols significantly increase the wickability of the nylon.

In addition to the indicated alcohols, other hydroxy-bearing compounds may be grafted such as, for example, furfuryl alcohol, tropolone, 2-hydroxy( 2,2,1)-bicyclohept-5-ene, propargyl alcohol, 2-methyl-3-butyn-2-ol, 2,2-dihydroxymethyl- (2,2,1 )-bicyclohept-5-ene, 3-hydroxycyclopentene.

It is desirable to graft sufiicient modifier so that, after hydrolysis, there remains at least about 100 equivalents of hydroxyl groups per million grams of polymer. The preferred range is from 500 to 2000 hydroxyls, although useful results are often obtained with 5000 or more hydroxy groups. These graft copolymers bearing hydroxy! groups have improved dyeability, especially when using acidic dyes. They have reduced static propensity as compared to unmodified polymer, and in addition are more wickable. They may be cross-linked by treatment with formaldehyde, diisocyanates, or diepoxy compounds, whereby they are rendered more resilient, infusible and water repellent. When post-reacted with perfluorocarboxylic acids they become soil repellent and oleophobic.

Other compounds suitable for post-reaction with grafted hydroxyl or carboxyl groups are diepoxides such as: butadiene diepoxide, dicyclopentadiene diepoxide, vinylcyclohexene diepoxide, divinylbenzene diepoxide, diglycidyl ether.

EXAMPLE 10 Four Samples, 10A, 10B, 10C and 10D, of a 66 nylon fabric are irradiated with the equipment and in accordance with the technique of Example 1. Prior to irradiation, three of the samples are immersed in solutions of chlorine containing monomers as identified below.

Sample 10A: p-chlorostyrene 15 parts b y weight of the solution Benzene parts b y weight of the solution Sample 103: p-chlorostyrene 15 parts b y weight of the solution Maleic anhydride 5 parts b y weight of the solution Benzene 70 parts b y weight of the solution Sample 10C:

Vinylidene chloride Vinyl acetate 85 parts b y weight of the solution 15 parts b y weight of the solution Sample 10D is employed as a control, i.e., it is irradiated without being given any coating. Each sample is subjected to a radiation dose of 33 Mrad. Thereafter each sample is subjected to l0 consecutive standard washings. From a chlorine analysis of each sample the amount of each modifier bonded to the fabric is calculated. These analyses are listed in Table 7. The number of equivalents of halogen per million grams polymer are also calculated.

It is thus apparent that approximately 0.5 percent of each modifying agent is chemically bonded to the fabric under the influence of the high energy particle bombardment.

A strip of Sample 10C, 1 X 6 inches, is held vertically over the flame from a match; the ignited fabric is self-extinguishing.

'When the test is repeated with control Sample 10D, the sample is completely consumed.

EXAMPLE 11 Six samples of nylon taffeta, coded 11A to l 1F, are soaked in water for 1 hour at 60 C., followed by a methanol soaking for l hour at 60 C., thus preswelling the fiber. The samples are then soaked in the solutions indicated in Table 8, for a period of 20 hours. The samples are placed in polyethylene bags, each containing about 20 ml. of a grafting solution, sealed with Scotch tape and irradiated for the specified dosage, using the 2 Mev Van de Graaf accelerator. After a 1 hour lag time following the irradiation, the samples are extracted in a Soxhlet extractor, using the solvents indicated in the table. After rinsing in water, the fabrics are dried over M0,, and the weight gain is determined. The results of the determination are indicated in Table 9. For comparison, sampics 1 10, H, l are padded with a coating of polyvinyl chloride deposited upon it from solution; due to the high molecular weight of this modifier compared to the monomers used for samples 1 1A to 1 1F, no penetration is attained.

lt u

in tetrahydrofuran 5% polyvinyl chloride in tetrohydrofuran AA n Following the grafting and washing, fabric sample 11F is analyzed to confirm the presence of chlorine. A positive test is obtained, showing 2.05 percent chlorine on the fabric. The samples are then tested for flammability, following the method described in Manual and Yearbook of AATCC, 1954, page 120-123, the method consisting of subjecting a 1.5 in. X 6- inch fabric sample, tilted at an angle of 45 in a metal frame, to a standardized flame, and visually observing the flammability. (Method is coded AATCC 33-62). These results are listed in Table 9, along with the equivalent concentration of grafted halogen.

( l Items marked ND are not determined. (2) Calculated from weight gain. (3) Calculated from C1 analysis.

It is noted that Samples 110, H, 1, although coated on the surface with polyvinyl chloride, showed increased flammability with increasing amounts of polyvinyl halide. This is thought to be due to the fact that at least some penetration of the fiber by the vinyl halide is required in order to impart satisfactory, non-flammability. It is also noted that Sample 11C with 14.2 percent weight gain, is flammable. Thus excessive amounts of grafted vinyl halide are not desirable.

It is also of interest to compare the weight gain of Sample 1 IF (5.9 percent) with the weight gain of Sample C of Example 10 (0.73 percent). The same modifier is used in each case, with a much larger dose of irradiation for Sample 10C which usually increases the amount grafted. The greater amount of polyvinyl chloride grafted onto 1 1F is thought to be due to the fact that the nylon is preswollen prior to exposure to the modifier, so that a high degree of penetration is obtained.

Three denier per filament nylon tow (without preswelling) is modified with 75 percent vinylidene chloride by the technique described in Example 8 using a dosage of l Mrad. Tetrahydrofuran is employed to extract unreacted monomer. Fabric is produced from the modified staple by conventional means.

Observation of the treated fabric during attempts to ignite it indicates that non-flammability of fabric is caused by evolution of hydrogen chloride at the melting temperature of nylon, combined with favorable viscosity of the melt, which forms foam. This foam excludes air and dilutes and cools volatile combustible degradation products of nylon below their ignition point, even though the molten polymer itself is flammable. Excessive amounts of grafted vinyl halide appear to lower the viscosity of the polymer during the ignition-melting process so that the foamed melt drops away from the fabric or filament and does not quench the flame. Thus, flammable fabrics are obtained when more than about 15 percent of polyvinyl chloride is grafted.

EXAMPLE l2 Non-polymerizable halogen-containing compounds are also useful in producing a flame-resistant fabric. Samples of nylon taffeta, 12A to 12D, are soaked in the liquids indicated in Table 10 for several hours at room temperature. They are then wrapped in aluminum foil while dripping wet, and exposed to electrons from the Van de Graaf accelerator, for a total dose of 60 Mrad. They are then extracted in a Soxhlet for 24 hours, using ethanol solvent. The per cent halogen, based on fabric weight, is determined and is indicated, along with the treating agent in Table 10. The halogen equivalents per 10 gram are calculated. Attempts are made to ignite the fabric samples with a burning match, without success. Nylon samples given the same soaking and extraction treatment, but without the irradiation, are readily ignited with a burning match.

TABLE 10 Sample Treating Halogen Equivalents Ignited No. Agent (on fabric) Halogen/10g By Match 12A carbon tetra- 1.18 332 no chloride 12B chloroform 1.55 436 no 1 2C tetrachlorol .52 428 no ethylene 1 12D methylene not bromide determined no When the test is repeated, using fabric samples prepared from nylon staple, similar results are obtained; when the staple samples are subjected to quantitative test, described in Example l 1, they are all found to be non-flammable.

The preferred saturated compounds for producing flameproof fabrics are the chain-transfer agents, especially those containing at least one and preferably several halogen atoms in the molecule, e.g. carbon tetrachloride, chloroform, methylene bromide, and the like. Compounds with high chaintransfer constants are preferred. Chlorine and bromine containing compounds are preferred to those containing iodine and fluorine. It is desirable to pre-swell the polymeric sub strate before or during impregnation with the halide-bearing compound. Samples preswollen before impregnation require a lower irradiation dosage to graft an equivalent amount of halogen.

The unsaturated vinyl halides are particularly preferred for producing flame-resistant fabrics, since large amounts are readily grafted using small doses of irradiation, thus contributing to low cost and efficient throughput. The preferred halides preferred range, however, is from 200 to 700 equivalents although modifications as high as 2,000 equivalents are often useful. It is usually desirable to avoid grafting as much as 3,000 equivalents of halogen.

EXAMPLE 13 A 14 X 9 inch nylon fabric Sample 13A is sealed in a polyethylene bag with 30 m]. of hydroquinone-stabilized, freshly distilled acrolein, and soaked for 24 hours. While still sealed in the bag, it is irradiated to a dose of l Mrad using the Van de Gruuf electron accelerator. Following the irradiation, the sample with the grafted acrolein is Soxhlet extracted with ucclunc for 24 hours and vacuum dried over P The weight gain is 4.5 percent, and the fabric has a log R of l2.4, as compared with a value of over 13.3 for an unmodified control. The test fabric also is somewhat stiffer than that of the control.

When the test is repeated, with a new nylon Sample 133 using inhibitor-free acrolein, and a does of 6 Mrad, a weight gain of 25.0 percent is obtained. When Fabric 138 is heated to a temperature of 180 C., it appears to become somewhat cross-linked and is then resistant to hole melting.

When nylon fabric Sample 13B is heated for 2 hours at 70 C. in a solution of ethanol plus p-toluene sulfonic acid, it is believed that acetylization takes place. The sample treated in this manner shows a large increase in wickability, and a small change in electro-resistivity. Similar results are obtained with a fabric of polyethylene terephthalate filaments.

In addition to acrolein, other unsaturated aldehydes are readily grafted to polymer substrates, such as for example, methacrolein, furfural, acroleindiethylacetal and the like. Saturated graftable aldehydes include formaldehyde, acetaldehyde, glutardialdehyde, benzaldehyde, dextrose and the like. It is desirable to graft on at least about 100 equivalent of aldehyde groups per million grams of polymer to produce noticeable effect; the preferred range is from 500 to 2,000 or more equivalents, whereas as much as 5,000 equivalents are desirable for some uses.

As aldehydes, these graft copolymers have improved dyeability. In addition, they may be cross-linked through an aldol condensation or other cross-linking reaction whereby melt resistance is improved. These graft copolymers may also react with compounds containing hydrophobic groups e.g., stearamide) whereby they become water repellent. Their adhesion to elastomer and vinyl plastics is improved over the adhesion of condensation polymers, when contacted with aldehydercactive adhesives.

EXAMPLE 14 Nylon taffeta samples are soaked in a solution of 15 ml. of methanol and 15 ml. of 4-vinylpyridine, under the conditions shown in Table 11. Following the soaking, each sample is packaged in a polyethylene bag and is irradiated at the soaking temperature, with the dose shown. Each sample is washed 4 times in distilled water at 80 C. and the weight gain (Table l l is determined upon the dried fabric.

Sample 14C, having grafted pyridine groups, is heated at the boil for one-half hour in a solution containing 2 drops of concentrated sulfuric acid in 100 ml. of water. The resulting fabric is highly wickable, and has a log R value of 55 percent RH of 8.5. The wet crease recovery is markedly improved in comparison with an unmodified control fabric.

Other amines are readily grafted to condensation polymer substrates, such as for example, allylamine, vinylamine, diamino-octadiene, N.N-diallylmelamine and the like. When N,N-diallylmelamine is grafted to polyumide fabric, followed by cnmslinking with aqueous formaldehyde, a fabric with increased resilience and resistance to hole melting is produced.

EXAMPLE 15 Although a wide variety of amines can be grafted to condensation polymer substrates, the particularly preferred amines for conferring improved acid dyeability are those which are sufficiently heat stable so that they do not cause excessive yellowing when the fabric is subjected to heat-setting conditions. The preferred modifiers are those nitrogenous organic bases, containing carbon-carbon unsaturation either isolated or conjugated with a carbonyl function, and which bear amine groups in either of the following configurations: (A) primary amine groups, with no hydrogen atoms on the carbon adjacent to nitrogen, and (B) tertiary amine groups, with no hydrogen atoms on the carbon atoms beta to the tertiary nitrogen. The grafting of these compounds is illustrated in this example.

Nylon taffeta samples are soaked for 20 hours in a solution containing 0.54 grams of the preferred amine, 0.25 grams of acetic acid and 1.6 ml. of water per gram of fabric. After soaking, the wet fabrics are wrapped in aluminum foil and irradiated with a dose of 5 Mrad. The samples are then washed at 60 C. with Tide for one hour, rinsed once at 60 C. for one hour, and twice at room temperature for 10 minutes. After drying for 5 minutes at C. the samples are weighed to determine the weight changes accompanying grafting.

The fabric samples are dyed by boiling for one hour in a solution consisting of 50 ml. of water, 0.l g. of dye, and 5 ml. of 10 percent aqueous potassium acid phthlate solution per gram of fabric. The dyed samples are then washed by 15 minutes in Tide solution at 60 C., rinsed twice with distilled water, and dried by heating to 90 C. in a forced air oven for 5 minutes.

The amount of dye taken up by each sample of saturation dyed fabric is determined by dissolving a weighed sample of the fabric in formic acid, and measuring the optical density of the solution at a wave length appropriate to the dye used; in this case, the wave length is 330 mu for anthraquinone blue GA (C.l.Acid Blue 58) dye. Quantitative results are obtained by comparison with standard solutions of the dye. The values obtained, along the number of amine ends grafted are indicated in Table 12. For purposes of comparison, an unmodified, unirradiated control nylon has a dye uptake of 1.90 percent.

TABLE 12 Amine Ends introduced] 1 Ogm.

Dye Uptake Compound Grafted Sample 3,3 dimethyl-4- dimethyl-aminol butene 2,2 dimethyl-3- dimethyl-aminopropyl acrylate N-acrylyl tetramethylethylene diamine N,diacrylyl tetramethylethylene diamine N-(2,2-dimethyl-3- dimethyl-aminopropyl) acrylamide "Excess homopolymer not removed by scour, but removed in acidic dye bath.

EXAMPLE 16 The process of this invention is useful for introducing amine groups to improve the dyeability of condensation polymer substrates using non-polymerizable compounds, in addition to the vinyl amines shown hereinabove.

One sample of 66 nylon fabric (Sample 16A) is immersed in a solution of 50 parts hexamethylene diamine and 50 parts water. A second sample of this same fabric (Sample 168) is immersed in liquid bis( 3-aminopropoxy)-ethane. These samples are then irradiated along with an untreated control (Sample 16C) with the equipment and in accordance with the technique of Example 1, to a total dosage of 33 Mrad. Each sample is subjected to l5 standard washings. Separate 10 gram portions of each of the samples are then dyed competitively with an acid dye and with a basic dye for 1 hour at a temperature between 95l00 C.

Acid dye bath composition:

llU Punt Milling Red 35 dye A wetting agent sold by the Rohm and Haas Company of Philadelphia, Pa, under the name of"Triton Xl 00.

TABLE 13 Sample Acid Dye (red) Basic Dye (green) l6A Much darker than control 163 Darker than control Much lighter than control Much lighter than control The control, Sample 16C, shows only slight change in its dyeability over a swatch of the original, non-irradiated and uncoated fabric. Cross sections of the acid-dyed filaments of Sample 16A show uniform dyeing throughout, proving that the diamine penetrated the fiber before grafting.

The receptivity of the fabric toward basic dyes may be improved by substituting an acid modifier (such as adipic acid) for the amines employed above; in addition, the adipic acid grafted nylon has a softer hand then untreated control.

In order to effectively improve the dyeability of condensation polymer fabrics, it is desirable to graft a minimum of 50 equivalents of amines per million grams of polymer; it is preferred, however, to graft 120 to 3,000 equivalents. Most satisfactory results are obtained when the amines penetrate throughout the entire thickness of the fiber; thus, deep shades are obtainable, and there is no danger of color change as the fabric wears, such as occurs when merely ring or surface dyeing is obtained. As a minimum, the dye should penetrate at least 10 percent along the radius in 2 denier per filament yarn (e.g., a distance of 0.8 microns in a yarn of 16 micron diameter). The same minimum distance (i.e., 0.8 microns) is adequate on yarns of higher denier per filament.

EXAMPLE 17 A sample of fabric woven from continuous filament polyethylene terephthalate immersed in liquid bis (3- aminopropoxy)ethane and thereafter irradiated in the equipment and in accordance with the technique of Example 1 to a total dosage of 33 Mrad. The coated sample, an uncoated, irradiated comparative control and a swatch of the original fabric are subjected to 15 standard washings. They are thereafter immersed for one hour at 95l00 C. in the acid dye bath of Example 16. After thorough rinsing it is observed that neither of the comparative control samples is affected by the dye. The coated, irradiated fabric dyes a bright red. A microscopic examination of the cross section of the dyed fibers discloses that they are ring dyed."

EXAMPLE 18 The process of this invention may be employed to graft a dyestufi directly to a condensation polymer substrate. This process is illustrated in the following example.

A dyestuff is prepared by reacting a dye containing an amino group with methacrylyl chloride, to form the unsaturated dye l-(Z-methacrylamidophenylazo)-2-naphthol. In the preparation of the methacrylyl derivative, a solution of 6.6 g. of l(p-aminophenylazo)-2-naphthol in 160 ml. of benzene is cooled to C. and 2.9 g. methacrylyl chloride in 40 ml. benzene is added slowly. The reaction mixture is allowed to warm to room temperature, then heated slowly to reflux. After refluxing 4 hours, the contents are cooled and filtered. The filtrate is concentrated to one-fourth volume and filtered. The combined solids are extracted with acetone, which is then evaporated to yield the dye. The dye product is recrystallized from percent acetic acid; it has a melting point of 18 1 1 83 C. The parent dye, l-(p-aminophenylazo)-2-naphthol, is prepared by diazotizing pnitroani.line and coupling to 2- naphthol. This product is then reduced by sodium sulfide and the product purified by the hydrochloride; the melting point being 136-l44 C.

A swatch of nylon fabric is dyed at 82-88 C. for 1 hour with the above unsaturated dye, in a bath containing 2 percent of the sodium salt of a long-chain alcohol sulfate, 1 percent trisodium phosphate, 1.0 percent dye, based on weight of fabric. The bath ratio (by weight) is 40 parts liquor to 1 part fabric. Following the dyeing, the fabric wetted with the dye is irradiated (exposure of 5 Mrad) using the 2 Mev Van de Graafi electron accelerator. The dyed irradiated fabric is then subjected to repeated extraction with boiling dimethylformamide to remove ungrafted dye. The fabric with irradiationgrafted dye has a much deeper shade than an irradiated, un-

treated control, and also a much deeper shade than a dyed, ex-

tracted control that was not irradiated.

Thus, by the process shown in this example, suitable unsaturated compounds containing suitable chromophoric groups may be grafted to fibers of condensation polymers. Typical chromophoric groups are -N N, C C C N, C =O,andN =0.

These chromophoric groups will usually be present in conjugation and the color value of the group will usually be modified by one or more substituents, as is well known to those skilled in the art. Suitable auxochrome groups will usually be substituted, in order to increase both the tinctorial value and the substantivity of the dye. However, since the process of this invention permits direct chemical bonding of the dyestuff to the polymer substrate, the substantivity of the dye is of minor importance. Thus, dyes may be used which ordinarily produce unsatisfactory shades on condensation polymer substrates. Dyes which may be used include the nitroso, nitro, monoazo, disazo, trisazo, and tetrazo dyes. Stilbene, pyrazolone, ketoneimine, diand triphenylmethane and xanthene dyes are effective. Acrydine, quinoline, thiazole, indimine, indophenol, and azine dyes may be employed. Aniline black and the related dyes are also useful, as well as oxazine and thiazine dyestuffs. Sulfide dyes, known as sulfur dyes, are effective as well as the hydroxyketone, hydroxyquinone and hydroxylactone dyes. Anthraquinone dyes of the acid, mordant and vat types are suitable, as well as the arylido quinone and indigoid dyestuffs.

It will usually be desirable to react a readily graftable monomer with some functional group in the dyestufi' molecule, whereby the dye is readily attachable to the polymer substrate, avoiding excessive doses of radiation. Such excessive doses are usually to be avoided, since the shade of the dyestuff may be affected by the irradiation. Alternatively, some dyestuffs may be grafted directly, without the introduction of additional unsaturated groupings, especially when unsaturation is already present in the molecule.

EXAMPLE 19 Three swatches of nylon fabric, 19A to 19C, are soaked in treating solution as indicated in Table 14. After the soaking period, they are wrapped in polyethylene film, and are irradiated to the indicated dosage. Following the irradiation, they are treated in a Soxhlet extractor for 24 hours with the solvent listed.

I 9C redistilled vinylisocyanate 24 25 cyclohexane Following the extraction treatment, the sample swatches are 5 When the test is repeated, soakin' g the nylon fabric in 5 perdried and weighed. Strips one inch wide of the grafted fabric cent aqueous methylene bis-acrylamide, at a temperature of are then cured in contact with various rubber substrates. Fol- 80 C., followed by irradiation with a dose of l Mrad, a 2.8 lowing the curing, the fabric is peeled back 1 inch, then fabric percent weight gain is noted after ungrafted polymer has been and rubber base are clamped in an Instron tester, and the removed. The modified nylon is insoluble in formic acid and force required to strip the grafted fabric from the cured infusible to the touch of a cigarette ash. A second application rubber is measured in pounds per inch. The results are listed in of the solution followed by similar irradiation dose results in a Table I5, along with the results obtained with numerous other 7 percent total weight gain. The fabric appears to be more m fi which. when grafted {0 nylon as discl s resilient than the unmodified nylon. The fabric is highly hereinabove or following the procedure of this example, ini k bl b t doe not have the old, lamm li h d crease adhesion to rubber. in the wet state that often accompanies high wickability.

TABLE 15 Tear Percent adhesion, Modifier grafted lbs/in. Elastomer Glycidyl methacrylate 15.9 5.2 Natural rubber. Glyeidyl methacrylate plus methyl acrylate. 64. 5 6.0 0. Vinyl isocyanate 13. 3 10. 0 GRS rubber. Butadiene. 9.9 40.0 Do. Butadiene plus styrene 34. 2 40. 0 Do. Butadieue plus acrylonitrile l6. 5 40. 0 Do.

Acrolein 26.2 3.0 Butyl rubber. \inyl alcohol 23. 0 3. 5 Neoprene rubber. 191 Episulfide of glycidyl methacrylate 23.4 10.0 G S rubber.

In Table l6 are indicated the curing conditions under which EXAMPLE 21 the treated fabrics are cured to the rubber slab, and in addi- Other di-unsaturates may be grafted to improve the tion the adhesion of control (unmodified) nylon to the various resilience of nylon, presumably by a cross-linking mechanism. elastomers. Nylon Samples 21B and 21C are grafted with butadieneacrylonitrile and butadiene-styrene mixtures, following the techniques disclosed hereinabove. After irradiation grafting, TABLE16 the samples are extracted with benzene to remove excess homopolymer, and are then tested for crease recovery with the results shown in Table 17. Included also is an untreated Elast. Curing Conditions nylon control, Sample 21A. Both of the grafted samples show T Adh U d an improved crease recovery both wet and dry, s compared to Time, emp., esron, nmo to Elastomer min. Nylon Comm! lbs/in the unmodified control.

TABLE 17 bb 45 MI 6.8 Sig 45 18 Sample No. 21A (control) 218 21c buty 45 1 53 1 3 Modifier none butadierie/ butadiene 4 l4 1 1.7 acrylonrtrile lstyrene neoprene 5 f d none 68 25 Crease recovery warp Dry 68 s5 81 Wet 68 85 81 55 The vulcanized test samples are prepared as follows: strips It is often desirable that grafting conditions (e.g., temperaof fabric of 1 inch X S-Ydnch of the test materials are laid on ture, dose, etc.) be adjusted so that residual unsaturation uncured 5--% X 6 inch rubber slabs. The whole system is put in remains after the grafting step is completed, thereby leaving a hot mold and cured for the stated time at the specific temthe double bonds available for further crosslinking or for imperature,underamold pressure of 1l4.9lbs/in. proving adhesion. This will not ordinarily require unusual Thus, according to the process of this invention, the fabric precautions; suitable conditions have been disclosed prepared from condensation polymer has improved adhesion hereinabove. to various types of elastomers, when certain vinyl monomers It has been shown that a variety of (ii-unsaturated modifiers are grafted thereto; for GRS rubber, butadiene, butadieneare useful for cross-linking reactions. Often combinations of styrene and butadiene-acrylonitrile combinations are espemonomers are more effective than a single one. Examples of cially effective. suitable modifiers are butadiene, butadiene plus styrene, bu-

tadiene plus acrylonitrile, isoprene, chloroprene, methylene EXAMPLE 20 bisacrylamide, divinylstyrene, divinylbenzene and the like. Usually monomers with short stiff chains between the vinyl A sample of 66 nylon fabric is immersed in liquid diallylbenzene phosphonate. It is then irradiated with electrons accelerated by the 2 Mev generator to a total dosage of 40 Mrad. It is given 15 consecutive standard washings. The diallylbenzene phosphonate coated sample displays a greater degree groups are more effective than those with flexible chains. improved adhesion has been described in terms of adhesion to elastomers, but improved adhesion to other substrates is readi- 1y obtained. For example, nylon batting modified with a 46.5 percent graft of glycidyl methacrylate shows improved adhesion in polyester resin laminates. Thus, following the procedure shown in this example, condensation polymer fabrics and filaments may be treated to improve adhesion not only to elastomers but also to vinyl plastics, papers, laminating resins, adhesives, inks and film coating compositions and the like. In effect, a pennanent anchor surface" has been grafted to the polymer substrate.

EXAMPLE 22 Nylon fabric Sample 22A is soaked for 24 hours at room temperature in a solution of 40 percent glycidyl methacrylate in methanol. After soaking, the fabric is squeezed between layers of filter paper and passed through a clothes wringer, then wrapped in aluminum foil. The sample is irradiated at room temperature under the beam of the 2 Mev Van de Graaf electron generator for a total dosage of 5 Mrad. After exposure, the non-grafted material is removed by a 24 hour Soxhlet extraction with methylethylketone. After drying over P a weight gain of 4.0 percent is observed.

The test is repeated, using nylon fabric samples 228, C, D, and E. The treating solutions are mixtures of glycidyl methacrylate (GMA), methanol and water, as indicated in Table 18. The soaking time is indicated in the table. These samples are irradiated in individual polyethylene bags containing 50 ml. of the treating solution. Following irradiation at the dose indicated in the table, they are subjected to the same extraction treatment as Sample 22A. After extraction, the weight gains are determined (Table 18 Fabrics 228, C, and D are white and have a soft and silk-like hand. Fabric Sample 22E is stiffer than unmodified nylon, has a pleasant dry hand, and shows improved adhesion to rubber when tested according to the procedure of Example 19.

Other epoxy compounds are also suitable for grafting to polymeric substrates; for example, 4.1 percent butadiene monoxide is grafted to nylon using an irradiation dosage of 6 Mrad. Other suitable compounds are vinyl glycidyl ether, allyl glycidyl ether, N-vinylcyclohexene monoxide and the like. The epoxide groups grafted to the nylon via attachment of the compounds of this example improve adhesion to various rubbets.

EXAMPLE 23 A swatch of 66 nylon taffeta fabric, coded 23A, of 2.4 g is sealed in a polyethylene bag along with a solution of 30 g vinylstearate in 40 ml. methanol plus 30 ml. dioxane. After heating for 45 minutes at 70 C., the whole system is irradiated while hot with 2 Mev electrons for a total dosage of Mrad. After a hold-up period of one hour the fabric is treated with benzene in a Soxhlet extractor for 24 hours, followed by a 30- minute wash in water (70 C.) containing 0.3 percent Tide detergent. Afier rinsing in water and drying in a vacuum desiccator over P 0 a weight gain of 2.7 percent is obtained. The fabric has a wax-like hand. The water repellency as determined by A.A.T.C.C. method 22-52, has a rating of 50-70 vs. 0-50 for control.

The percentage surface area expansion afier wetting of the fabric is 4 percent, vs. 4.7 percent for unmodified control nylon.

The above procedure is repeated, using a fresh swatch of nylon, 23B, and soaking it in 100 percent vinyl stearate for 60 minutes at 80 C., followed by irradiation to a dose of Mrad. The weight gain is 17.1 percent. The fabric has a waxlike hand. The greater part of the vinylstearate is grafted on the surface of the fabric. The percentage surface area expansion after wetting is 2.6 percent.

Suitable compounds for improving the water repellence of shaped articles of synthetic linear condensation polymer include the acrylates of long chain aliphatic alcohols, the vinyl esters of long chain aliphatic acids, and vinyl ethers of long chain aliphatic hydrocarbons.

EXAMPLE 24 A one-mil film of biaxially oriented polyethylene terephthalate is wet with monomeric glycidyl methacrylate, wrapped in 2-mil aluminum foil and irradiated with 2 Mev electrons to a dosage of 5 Mrad. The film is then heated for one hour at C. and finally extracted to constant weight with acetone at room temperature. A weight gain of 2.2 percent is obtained. The film is unchanged in appearance. It is highly adherent to polymeric epoxide adhesives and adhesion is not lost upon immersion in water.

EXAMPLE 25 Following the procedures described hereinabove, specified amounts of various water-repellent compounds are grafted to nylon and polyethylene terephthalate fabrics, as indicated in Table 19 The increase in water repellence is indicated by the increased length of time required for a drop of water placed upon the fabric to disappear. Values for comparative unmodified controls are included in Table 19.

By the process of this invention, certain fluorine containing compounds are grafted to fabrics of condensation polymer whereby the fabrics are rendered permanently resistant to wetting or soiling with oils, hydrocarbons and other common organic solvents, as well as being water-repellent. This modification is illustrated by the following example.

EXAMPLE 26 A scoured nylon taffeta sample 26A is soaked for 15 minutes at room temperature in 20 ml. of an 8 percent diethyl ether solution of alpha, alpha-dihydroperfluorooctyl acrylate, which had been prepared as described in Example 4 of US. Pat. No. 2,642,416. After soaking for 15 minutes at room temperature, the nylon sample is irradiated, while wet, with 2 Mev electrons for a dosage of 3 Mrad. After cooling, another 20 ml. portion of the 8 percent solution is added, followed by a second irradiation using the same dose; the process is repeated a third time to give a total dosage of 9 Mrad. A total of 60 ml. of the 8 percent solution is used. The sample is then extracted for 24 hours with each of the following solvents: tetrahydrofuran, carbon tetrachloride, perchloroethylene, and dimethylformamide; the sample is then boiled for 8 hours in 0.3 percent Tide solution. After these extractions, the sample is tested for oil repellency using the following test:

Drops of mixtures of a mineral oil (Nujol) and n-heptane are placed on the fabric, and the composition is noted which contains the highest percentage of n-heptane which does not wet the fabric under the drop. The rating corresponding to that composition is considered the oil repellency of the sample.

Oil Repellency Rating Scale Oil Repellency Percent n-Heptane in A rating of 100+ is observed for 26A, vs. a rating of for an untreated control, 26B. When a nylon sample 26C is treated with the polymer of the above perfluorooctyl acrylate, without irradiation, a rating of 100+ is observed; however, after four 15 min. Tide washes (a less severe treatment than given to 26A), the rating drops to 0.

The same modifier is applied to a tow following the procedure detailed in Example 8. A dosage of 3 Mlrad is applied. The ether solvent is removed prior to irradiation and the tow is given 3 successive soakings and irradiations to build up the modifier. Perchloroethylene is employed as the wash. Staple cut from the tow is processed in the conventional manner.

The test is repeated, using a fabric of polyethylene terephthalate taffeta, wherein soaking is carried out for 15 minutes at room temperature, followed by slowly raising the temperature to 95 C. in a system sealed to prevent escape of monomer. The material is irradiated at this temperature to a dose of 5 Mrad. The process is repeated three times, as before. After extraction for 24 hours using carbon tetrachloride solvent, similar oil repellency is observed.

Grafted fluorocarbon compounds are also useful in imparting resistance to soil, and improving ease of soil removal, as shown by nylon sample 26D which is soaked in a solution of 20 parts ethyl 2,3,8-trihydroperfluorohepten-2- oate, 20 parts water and 60 parts methanol; and nylon sample 26E, which is soaked in a 20 percent solution of perfluoroheptene-l in ether.

The perfluorohepten-Z-oate is prepared as follows, using the synthesis of McBee.

In a 300 ml. three-necked flask fitted with a stirrer, funnel and condenser, 13 grams (0.125 mols) malonic acid is added to l00 ml. pyridine. The mixture is stirred at room temperature while 28 grams of C aldehyde in 100 ml. of toluene is added. After completing the addition, the mixture is refluxed for 6 hours, cooled and poured onto 400 grams of ice and 50 ml. of concentrated sulfuric acid. Three layers form; both the lighter and heavier water layers are shown to contain product. They are removed, combined and evaporated under vacuum. The oil is taken up in bicarbonate and ether, washed twice and acidified, and is then shaken with 3 100-ml. portions of ether. The ether solution is dried and the ether evaporated to give crude, solid acid. Recrystallized from benzene, white cubic crystals of 3-hydroxyoctafluoroheptanoic acid are obtained, melting at 63-64 C., (weight 21.6 grams, 62.9 percent yield).

The acid is esterified by refluxing with 20 ml. absolute ethanol and 40 ml. benzene in a flask fitted with a Dean-Stark water trap. One gram of para-toluenesulfonic acid is added. The reaction is completed in 12 hours and the mixture is evaporated in vacuum to remove alcohol and benzene (91 percent yield).

Crude ester from all sources (56 gm) is then distilled in a spinning band column to yield 46 grams of product boiling at 130 C., l22 mm.

The hydroxy ester is dehydrated by mixing 11 grams of phosphorus pentoxide with the ester and distilling through a spinning band column at reduced pressure. The ethyl octafluorohepten-Z-oate obtained has a boiling point of 92 C., under 28 mm. pressure.

The perfluoroheptene is prepared by a method analogous to that described by La Zerte, Hals, Reid and Smith, Jour. Am. Chem. Soc., 75, 4525 (1953) for the homologous perfluorobutene.

The soaking, irradiation and extraction procedure used for sample 26A is repeated for 26D and 265. These samples, along with non-irradiated control 268, are then subjected to a standard laboratory soiling test, with the results shown in Table 20.

TABLE 20 "Reflectance gives per cent of original light reflectance retained after the indicated treatment; all original reflectance measurements taken after two soiling cycles.

"'Composition and procedure of Wagg oily soil test given in Example 7 and is described by R. E. Wagg, J. Tex. Inst, 1952, T 515; this soil corresponds to soil from the skin, and to extraneous grease and oils. "Composition and procedure of Lambert dry soil given by: H. L. Sanders and J. M Lambert, J. Am. Oil Chem. Soc., 5, 153-159 (1950) May; this soil corresponds to vacuum-cleaner soils.

Compounds useful in modifying condensation polymer substrates so that they are resistant to oils, oily soil and dry soil are graft copolymers of unsaturated esters having the following general structures:

Also useful are unsaturated ethers having the following general structure:

R(CF CH OCH CH:

In these general formulas, X may be fluorine or hydrogen (when X is fluorine, the graft copolymer shows a higher degree of hydrophobicity and oleophobicity than when X is hydrogen), n is 3 to 17, and R may be alkyl or hydrogen and R may be alkyl. The lower alkyl groups are preferred, since long chain alkyls impart oleophilic properties. The grafted fluorine-containing portion of the copolymer should preferably be located on the surface of the structure but may be throughout the body of the base fiber.

The class of compounds which works best is the omegatluro type. These are superior to the omega-hydro compounds. It is also preferred for a high degree of oleophobicity that n be at least 7.

EXAMPLE 27 Fabric samples of various yarn description are soaked in a fluorocarbon alcohol, HCF -(CF CH OH. Thereafter they are simultaneously exposed in the equipment and in accordance with the technique of Example 1 to a total radiation dose of 33 Mrad. Uncoated comparative controls are irradiated at the same time. Samples of the test, control and original fabrics are given 15 consecutive standard washings. Results of a subsequent test for water repellence are listed below.

Drop diameter in inches afier 60 seconds.

EXAMPLE 28 Nylon samples with grafted 4-vinylpyridine are prepared, following the procedure of Example 14. Samples 28A and 28B have a weight gain, due to grafted 4-vinyl-pyridine, of 20 percent.

The polyvinylpyridine graft is quatemized by heating the fabric samples at reflux in 500 ml. of methanol and 50 grams of butyl bromide for 15 hours. The fabric samples are washed twice in hot methanol and once in water at 80 C. to remove any free butyl bromide and methanol. The weight gain after quatemization indicates that approximately 55 percent of the available pyridine groups have been quaternized. A control sample, 28C, not grafted with 4-vinyl-pyridine, is subjected to the butyl bromide treatment In addition, a control sample entirely untreated, number 28D, is subjected to the test. The

samples are identified in Table 22.

TABLE 22 Sample Sample Identification No.

28A Nylon with grafted 4-vinylpyri dine (4VP),

quaternized with butyl bromide 28B Nylon with grafted 4V1, not quaternized 28C Control nylon treated with but yl bromide 28D Control nylon, untreated Portions of these samples are tested for biological activity against a Micrococcus Pyogenes bacterium. Following the procedure described below, it is found that the grafted, quatemized sample, 28A, inhibits bacterial growth in 12 of the 1 6 samples tested, whereas no inhibition is noted with the various control samples 288, C, and D. The results of the tests are listed in Table 23.

It is noted that the inhibitory effects of the active grafi (sample 28A) are confined to the fabric itself. Growth occurs around the edges of the fabric, indicating that the active species does not diffuse, but remains attached to the fabric substrate.

The following procedure is used to test the fabric samples: 0.05 ml. of nutrient broth, containing a 1:10 dilution of Micrococcus Pyrogenes var. Aureus and 0.1 percent 2,3,5- triphenyl-2H-tetrazolium chloride, is pipetted to strips of fabric 1 X 2.5 cm. The tetrazolium chloride is added as an indicator of bacterial growth, since it is colorless in the oxidized state, but as the bacteria grow, it is reduced and becomes red. Control samples (nutrient broth and tetrazolium chloride, but no bacteria) are also tested. After the broth dilutions are pipetted to the fabric samples, the samples are placed on sterile nutrient agar plates. Both sterile" (boiled in methanol) and non-sterile nylon samples are tested. All plates are incubated at 37 C. for 16 to 18 hours, afier which they are examined for bacterial growth on the fabric.

When growth is observed on the fabric, the result is recorded as non-inhibitory. When no growth on the fabric is observed, the result is recorded as inhibitory.

This example shows that by the process of this invention, bactericidal compounds may be permanently attached to fabric substrates. This is most surprising, since it has always been thought that a bactericide, to be effective must be somewhat soluble in liquid media. The modification produced by the process of this invention, however, remains permanently attached to the fabric, so that it is retained permanently for the life of the fabric, through washing and wearmg.

EXAMPLE 29 A swatch of nylon fabric, 7 X 9 inches, is placed in a polyethylene bag containing ml. of 60% N-vinyl-pyrrolidone in water. The bag is sealed, and the fabric is allowed to soak for 10 ours at room temperature. The bag containing the sample is then irradiated, using the Van de Graalf electron accelerator, to give a dose of l Mrad. After a hold-up time of 1 hour, the fabric sample is removed and non-grafted homopolymer is thoroughly rinsed away using hot distilled water (80 C.). After rinsing, the fabrics are boiled for 30 minutes at C. in a pressure cooker, and dried. The fabric has a weight gain of 45 percent.

The fabric with grafted polyvinylpyrrolidone is then boiled for 30 minutes in a solution of 1 percent iodine in methanol, followed by a 5 minute rinse in methanol. An additional weight gain of 8 percent is noted, due to the formation of an iodine complex with the grafted N-vinylpyrrolidone. Three portions of this fabric are then placed in contact with growing colonies of two fungii, Chaetomium Globosum and Aspergillus Niger, and one bacterium, Micrococcus Pyogenes var. Aureus. A significant zone of growth inhibition is noted with all three samples. The growth inhibition is significantly greater than that obtained with an original 66 nylon fabric which was merely treated with the methanolic iodine solution.

When the test is repeated, using a fabric of polyethylene terephthalate with grafted N-vinylpyrrolidone, which is subsequently reacted with iodine, similar results are obtained.

Examples 28 and 29 show that according to the process of this invention, condensation polymer substrates can be prepared containing biologically active groups. In general, two broad types of products are shown by these two examples. For instance, Example 28 shows biologically active modifiers permanently attached. Typical compounds are the quaternary compounds prepared from butyl, benzyl and cetyl bromides, and grafts of poly-4- or poly-2-vinyl-pyridine with condensation polymers. In general, alkyl and/or aromatic quaternary compounds of a vinylpyridine graft on the condensation polymer are suitable. In addition to the vinylpyridines, other monomers may be grafted, which may be thereafter quaternized with alkyl or aromatic bromides to produce a biologically active compound. Suitable monomers are vinyloxyethylamine, triallylamine, and the like. N-vinyl-N-methylformamide may be grafied, and hydrolyzed prior to quatemizing. Other vinyl monomers containing reactive groups such as halogen, nitrile, or isocyanate may be converted to the amine product for quaternization. in fact, any monomer containing a group which is convertible to a quatemizable amine may be employed.

Alternatively, vinyl compounds with preformed quaternary groups may be grafted, to give chains grafted to the condensation polymer. Typical structures are illustrated below:

In addition to the above, modifiers bearing biologically active groups which are released slowly are useful. Such modifiers are illustrated by the graft of N-vinylpyrrolidone post-reacted with iodine, as shown in Example 29. Other such compounds are produced by grafting an unsaturated acid, e.g., acrylic acid, and post-reacting with biologically active metal salts to form a grafted salt of acrylic acid such as shown in some of the examples. Suitable metals for forming the salt are mercury, silver, copper and the like.

Extremely small amounts of biologically active compounds are required in order to effectively prevent the growth of bacteria, when these are permanently attached to fiber surfaces. From theoretical considerations, for example, it has been calculated that if all the biological activity is on the fabric surface, merely weight per cent is required. In general, it will, of course, be preferred to graft larger amounts of modifier than this. For example, 5-20 percent is usually suitable, although at times it may be preferred to go as high as 50 percent. For diffusible biological compounds, it is preferred to graft about 0.5 2 percent by weight; usually little added advantage will be obtained by grafting more than 50 percent.

The germicide-grafted fibers illustrated hereinabove are useful for bandaging, as sterile absorbents, and for germ-free linen, masks, curtains, rugs and the like, especially such as would be suitable for use in hospitals, etc. Clothing may be produced with is fungusand germfree and incapable of transmitting infection. In addition, development of perspiration odor may be prevented. The products produced by this process are also suitable for non-rotting and mildew-proof outdoor textiles such as fabrics (clothing) for tropical use, soils, awnings, tents, tarpaulins and the like. Many other advantages will be obvious to those skilled in the art.

EXAMPLE 30 The process of this invention is useful in reducing the alkaline sensitivity of polyester fibers and fabrics. lts effect is shown for polyester fabrics grafted with polyacrylonitrile, in Example 7; similar results are obtained when methyl methacrylate is grafted to polyester substrates as shown in this example.

Three samples of tropical worsted fabric prepared from polyethylene terephthalate filaments are immersed in 500 grams of a 50 percent solution of methyl methacrylate dissolved in propanol, and areheated at 90 C. for 30 minutes. The fabric samples are transferred to stainless steel pans containing 200 ml. of the soaking solution and are then irradiated for a dose of l Mrad at 90 C., using 2 Mev electrons. The grafted fabric samples are extracted with boiling acetone to remove unreacted monomer and unattached polymer, after which they are dried at C. Treating conditions, weight gains, and alkaline sensitivity of the fabrics are shown in Table 23. The alkaline sensitivity test is the same as that described for example 7.

terephthalate and 2 percent sulfonated polyethylene isophthalate; the fabrics are soaked in a 20 percent solution of methyl methacrylate dissolved in butanol, followed by the same irradiation dose. In this case, a weight gain of 1.1 percent after extraction, is observed. The alkaline sensitivity is only 0.61 as compared to an unmodified control fabric using the same polymer.

Methacrylate esters are particularly effective in improving resistance to caustic sensitivity, due to their own resistance to caustic hydrolysis. Thus, effective protection is obtained when from 1 to 4 percent of methyl methacrylate is grafted to polyester substrates. Also effective are the higher alkyl acrylates such as methyl, ethyl, propyl and the like; in general, the lower alkyl esters are preferred.

Acrylate esters are also advantageously grafted to polymer to substrates, and especially after a superficial hydrolytic treatment, provide fabrics of improved dyeability and resistance to soil. This embodiment is illustrated by the follow ing example.

EXAMPLE 31 A fabric swatch of polyethylene terephthalate tropical worsted (prepared from staple) is immersed in 150 grams of a 50 percent solution of methyl acrylate in propanol, and is heated at C. for 30 minutes. The fabric is transferred to a stainless steel pan containing 200 ml. of the above methyl acrylate solution, and is then irradiated at 90 C. for a dose of l Mrad. The grafted fabric, number 31A, is extracted in boiling methanol for 2 hours to remove unreacted monomer and ungrafted polymer, after which it is dried at 80 C. A weight gain of 4.6 percent is observed. The sample is then superficially hydrolyzed by boiling for 1 hour in 1 percent sodium hydroxide solution.

Three denier per filament polyethylene terephthalate tow is soaked in methylacrylate at 90 C. for 30 minutes. The tow is then irradiated without squeezing off excess liquid at 90 C. at a rate to provide dosage of l Mrad. Boiling methanol is employed as the wash" to remove unreacted monomer. Staple is cut from the tow. The structure can be hydrolyzed at any time after irradiation.

Following the above procedure, Samples 31B and 31C of polyethylene terephthalate fabric are prepared to contain 5 and 10 percent respectively of grafted methyl acrylate. The samples are superficially hydrolyzed by boiling in 1 percent sodium hydroxide as before. The treatment results in hydrolysis of the surface layers of grafted methyl acrylate, producing a residue of acrylic acid groups attached to the fabric substrate, in addition to some non-hydrolyzed methyl acrylate. The caustic treatment simultaneously forms the sodium salt of the grafted acid. When this product is tested for wickability, the rate of disappearance of a drop is much more rapid in the case of Samples 31B and 31C (less than 1 second) than it is for control Sample 31D (19 Seconds) which has not been modified except for the caustic boil-off. In addition, a laboratory laundry soil test (described in Example 7) shows a value of 17 for control versus 7 and 6 for the two modified fabrics, indicating a substantial improvement in rate of soil removal.

In addition to the above advantages, the dyeing rate with disperse dyes (test procedure in Example 8) is significantly increased for 318 and 31C.

Using procedures similar to those described above, nylon fabric sample 31D and polyethylene terephthalate fabric 31E are grafted with methyl acrylate.

Samples 31D and E and also corresponding control Samples 31F and G (without grafted methyl acrylate) are subjected to a 1 hour hydrolysis treatment at the boil, as indicated in Table 24, using 0.1 normal or percent sodium hydroxide solution. After the hydrolysis treatment, the fabrics are washed, rinsed in distilled water, dried and the log R determined; the results are shown in Table 24. Swatches of the test and control fabrics are dyed with a basic dye,

with the results also indicated in the table. These results show that the caustic treated samples dye to much deeper shades than the untreated ones.

(l) MA methyl acrylate An examination of the crosssection of fibers from Sample 31E showed a penetration of 3.2 microns out of a total diameter of 18.2 microns. This indicates that the methyl acrylate penetrated into the fiber before grafting.

The process of this example is repeated, using a sample of undrawn yarn 3lH, prepared from polybis(l.4-di-methylol) cyclohexane terephthalate. Skeins of this yarn are soaked in a 50:1 (Wt/Wt) bath of 50 percent methyl acrylate in butanol at 90 C. for 30 minutes, and are then irradiated for l Mrad in the padding solution using a Van de Graaf electron accelerator. After washing and extraction with acetone, followed by drying, a weight gain of 8.0 percent is noted. This product has improved dyeability, wet creased recovery, and the like, such as observed with fabrics from polyethylene terephthalate.

At a loading of 5 percent (weight gain), methyl acrylate accelerates the dye rate of polyethylene terephthalate at least by a factor of 2, and gives a deeper shade. Thus, this modified polyethylene terephthalate is dyeable at the boil with dispersed dyes, while still retaining hydrolytic stability and strength equivalent to that of the unmodified control fiber. Somewhat less effective results are obtained when ethyl acrylate is used instead of methyl acrylate, believed to be due to decreased fiber penetration. In general, it is preferred to use low molecular weight (especially lower alkyl)monomes in order to facilitate penetration. The improvement obtained by the methyl acrylate graft is sufficient to permit atmospheric pressure dyeing comparable to that attained with carrieror pressure-dyed control polyethylene terephthalate.

The important feature of the embodiment shown in this example is to use an acrylate monomer that may be hydrolyzed to provide a useful number of carboxyl groups. Higher alkyl acrylates as well as methacrylate esters are less effective due to their resistance to hydrolysis. However, alkyl ether acrylates are advantageously grafted to polyester substrates as shown hereinafter.

The procedure for Sample 31E is repeated, using polyethylene terephthalate fabric 311, and substituting Cellosolve acrylate (C,l-l,,O-Cl-l,CH,-OOC-CH (1H,) for methyl acrylate, as a 5 percent aqueous emulsion; the irradiation dose is l Mrad. The fabric is scoured in boiling acetone for 15 minutes to remove monomer and ungrafted polymer, scoured in 1 percent Tide solution for 15 minutes, and rinsed again in boiling acetone for 15 minutes. The weight gain is 2 percent.

Competitive dyeings of polyethylene terephthalate fabric and the same fabric with a graft of 2 percent Cellosolve acrylate show that the grafted fabric with is more deeply dyed than the control using a dye bath containing 2 percent (on weight of fabric) of blue dispersed dye of Example 8. The crease recovery of the test fabric is found to be 83 percent versus 78 percent for the untreated control.

A fabric, 3 1] prepared from polyethylene terephthalate modified with 2 percent Cellosolve acrylate, following the above procedure. It is then dyed at the boil with a dye bath containing 1 percent (on weight of fabric) of Sevron Blue 50 (CI. Basic Blue 22). The fabric dyes to a deep blue shade. Under the same dyeing conditions, an ungrafted sample of the same fabric acquires only a medium shade of blue. The crease recovery of the treated fabric is 69 percent, versus 61 percent for the untreated control, indicating improved wash-wear properties.

For dyeability at the boil, the preferred amount of grafted Cellosolve acrylate is in the range of 6-10 percent; a range of 1-10 percent produces useful improvements in crease recovery. Fabrics grafted with more then 10 percent of this acrylate usually have a waxy hand.

For useful improvements in dyeability, it is important that the grafted modifier penetrate into the fabric prior to the grafting operation. This is most readily accomplished by the use of low molecular weight acrylates such as Cellosolve acrylate.

Useful antistatic effects are obtained by grafting higher molecular weight acrylates, e.g., those containing more ethyleneoxy groups, to condensation polymer substrates. Such combination is illustrated by Example 1, wherein methoxydecaethylenoxy methacrylate is grafted to nylon substrates.

The process of this invention is useful for chemically grafting modifiers to the surface of substrates prepared from condensation polymers. The application and grafting of these polymeric modifiers is conveniently done upon the filaments, staple, or upon fabrics woven from said filaments. The most useful effects are produced when a thin, uniform coating of the polymeric modifier is applied to all the filaments. For apparel textiles, heavy deposits of coatings are usually to be avoided, since it has been found that upon irradiation said heavy coatings often result in a fabric that is stiff and boardy in character. Thus, it is preferred to limit the amount of modifier applied so that the stifiness of the fabric will not be increased more than about 50 percent, as compared to the original untreated fabric. Thus, drape, hand and other aesthetic properties of the original textile is retained.

To attain this uniform, controlled application of polymeric modifiers, it is desirable to apply said modifiers either as a solution, and emulsion or, if of sufficiently low molecular weight to have ready flowability, as a melt. A method of application is illustrated by the following example EXAMPLE 32 Methoxydecaethyleneoxy methacrylate polymer is prepared by heating 99.5 parts of the monomer with 0.5 parts of benzoyl peroxide on a steam bath at 100 C. for 1 hour. A gel-like polymer forms. A sample of a 66 nylon fabric (Sample 32A) is immersed in a solution-dispersion of the gel-like polymer in water. The sample is then exposed to irradiation with the equipment and in accordance with the technique of Example 1. Two control samples are employed. Sample 32B is immersed in the methoxydecaethyleneoxy methacrylate monomer while Sample 32 C is not coated prior to irradiation. Each sample is exposed to radiation dose of 33 Mrad. After consecutive standard washing and drying the antistatic pro perties (Log Resistivity) of each sample is observed. The observations are reported in Table 25.

TABLE 25 Log Resistivity Sample 1 washing 15 washings TABLE 26 Log Modi- Radiation Resis- Fabric fier Dose,Mrad tivity 33A D (contfiL) none none 13.1 333 D (cont.fil.) none 40 13.2 33C D (cont.fil.) A*"' 40 10.2 33D D (cont.fil.) A 20 10.9 3315 D (contfil) B""" 40 9.7 33F D (staple) none none 13.3 330 D' (staple) none 40 13.3 3311 D (staple) A 40 9.3 331 D (staple) A 20 10.2 33.7 D (staple) B 40 9.2 33K 66N" (staple) none none 13.3 33L 66N" (staple) none 40 13.4 33M 66N (staple) A 40 9.6

33N 66N" (staple) A 20 10.8 330 66N" (staple) B 40 9.3 33! GN'" (staple) none none 13.4 330 6N'" (staple) none 40 13.3 33R 6N'" (staple) A 40 9.6 335 oN" (staple) A 20 10.2 33T GN'" (cont. none none 13.2

D is polyethylene terephthalate.

' '66N is polyhexamethylene adipamide.

' 6N is polycaproamide.

A is liquid methox ydecaethyleneoxy methacrylate.

""B is a mixture of l6 parts of polyoxyethylene glycol of 20,000 mol. wt. (Carbowax 20,000) and 84 parts of water.

Antistatic properties are induced in all the modified fabric as noted. Use of the high molecular weight glycol as an aqueous solution prevents deposition of heavy coatings of polymeric material which would give a harsh hand to the fabric.

Sample 33D shows improved ease of removing oily soil (test procedure in Example 7); the difference between initial light reflectance and reflectance of 33D after standard soiling and washing is 1.1, as compared to a difference of units for control 33A. Sample 33D is more dyeable than 33A, with dispersed dyes (test procedure in Example 8).

EXAMPLE 34 Transparent polyethylene terephthalate film of 10 mil thickness is dipped into water containing 3 percent by weight of methoxydodecaethyleneoxy methacrylate. lt is irradiated wet, as in Example 1, to a total of 20 Mrads. The resulting film has improved antistatic properties (Log R 10.6-1 1.5 vs 13.1 for control) and is modified uniformly over the whole surface.

In Example 35 below, a polyurethane foam is modified by the process of the present invention. The preparation of polyurethane foam from a liquid foamforrning mixture of water and free isocyanate radical-containing polyurethane products resulting from the reaction (1 and alkyd or other active hydrogen-containing organic polymeric material and (2) organic compounds containing, as the sole reacting groups, a plurality of isocyanate groups, is described in German Plastics Practice by de Bell et a1. 1946, pp. 316 and 463-465.

EXAMPLE 35 A fine-pore, ester-type polyurethane foam is produced by mixing 23.3 grams of toluene diisocyanate containing percent toluene-2,4-diisocyanate and 20 percent toluene-2,6- diisocyanate into a composition of the following:

Polyester Resin 70.0 grams Polyoxyethylated vegetable oil 0.7 grams N-coco-morpholine 0.79 grams Water 1.7 grams Diatomaceous silica-average particle size 7-9 microns 2.0 grams Benzidine yellow pigment 0.1 grams The polyester resin" is the reaction product of diethylene glycol, adipic acid, and trimethylolpropane in a 13/ 1 3/1 molar ration. lts physical properties are:

Viscosity 16,000 cps. Acid No. 2.02 Specific Gravity 1.194 Water 017 Hydroxyl No. 66.8

After a holdup time of approximately 10 seconds, the mixture is placed in a mold where foaming occurs in about 30 seconds, being complete in about 3 to 4 minutes. The product is cured for about 8 hours at room temperature.

Samples of the fine-pore, ester-type polyurethane foam prepared as described above, are weighed, and then subjected to mechanical working to improve porosity (by pounding under water). They are next thoroughly soaked in a 15 percent by weight aqueous solution of a high molecular weight poly(ethylene oxide), Carbowax 20,000. Some of the samples are placed in polyethylene bags and irradiated at doses of l to 10 Mrad using the 2 Mev Vande Graaff accelerator. The sponges are washed overnight in cold water, and are then dried to constant weight. As noted in Table 27, all initially have excellent wickability (i.e., they very rapidly became water-soaked upon touching one'edge to the surface of the water) but only in the case of the Sample 35D does the property survive extensive washing. After washing, the samples are dried to constant weight. It is found that sample 35D has increased in weight by 40 percent over its initial weight. The sample has excellent hydrophilic properties upon rewetting. Untreated samples of the foam show poor wickability.

The slow dissolution of the coatings formed by low doses has the effect of gradually releasing some of the surface-active Carbowax. For some uses, this is advantageous, for example, in the commercial product designed for washing. However, the dose should initiate sufi'rcient cross linking and grafting to render the sponge hydrophilic for a reasonable length of time.

It should be noted that the modification of the foam throughout its bulk, without destroying its softness and its ability to retain water, is made possible by use of a low viscosity treating solution which carries the modifier to all internal and external surfaces without producing excessively thick deposits.

EXAMPLE E36 A sample of 66 nylon fabric is immersed in a solution of parts acrylamide and 90 parts water. It is then irradiated using the Van de Graaff electron accelerator, operated as described above, to a total dose of 40 Mrad. After standard washings, the dried fabric of the present invention retains a much stiffer hand than an uncoated, irradiated comparative control. Furthermore, the acrylamide-grafted nylon is more hydrophilic than non-grafted control samples and has a significantly higher wickability. Thus when samples of the acrylamidegrafted fabric of this example are boiled for 30 minutes in a bath having the composition (based on a fabric weight of 1 gram):

50 ml. water 0.1 grams of Perlon Fast Red 3 BS 002 grams of Triton X 100" 0.02 grams of ammonium hydroxide The cobalt dye of Example I ofGerman Pat. 743,l 5S (1943) "Octyl phenyl polyether alcohol sold by Rohm and Haas Corp. of Philadelphia, Pa.

the acrylamide-grafted nylon dyes rapidly to a deep shade whereas neither the original nylon nor irradiated (40 Mrad) nylon can be dyed as effectively under the same conditions using this bath.

Cross-sections of filaments removed from the dyed test fabric are deeply dyed throughout the entire cross-section, showing that the acrylamide has penetrated throughout the fiber prior to grafting.

EXAMPLE 37 A sample of 66 nylon fabric is immersed in a mixture of 30 which is not immersed in the liquid mixture prior to irradiation. Hot ashes from a burning cigarette are flicked onto the liquid-immersed, irradiated, washed fabric to determine its hole-melting tendency. Only a small brown stain results. Holes are immediately melted through the untreated fabric, whether irradiated or not. When dyed in the basic dye bath of Example 16, filaments of the dyed fabric show deep dyeing throughout the fiber cross section, showing that the modifier penetrated throughout each filament.

EXAMPLE 38 A series of fabric and yarn samples are prepared from the polymers listed in Table 28 and treated as shown in Table 29.

and terephthalic and sebacic acids, acid ratio 90:10

The poly(ether-urethane) referred to above is prepared by reacting poly(tetramethylene oxide) glycol (124.5 grams 0.12 mol) having a molecular weight of 1,035 with 10.50 grams (0.06 mol) of 4-methyl-m-phenylene diisocyanate with stirring in an anhydrous atmosphere for 3 hours at steam bath temperature. To this dimer with hydroxyl ends is added without cooling 30.0 grams (0.12 mol) of methylene bis(4- phenylisocyanate) dissolved in dry methylene chloride and the mixture is allowed to react for one hour at steam bath temperatures. The dimer" with isocyanate ends is allowed to cool and 400 grams of N,N-dimethylformamide is added. To this solution is added 3.0 grams (0.06 mol) of hydrazine hydrate dissolved in 26 grams of N,N-dimethylformarnide. The resulting polymer solution, which contained 28 percent solids, is dry spun in the usual manner to form elastic filaments.

TABLE 29.TREATMENT CONDITIONS Sample Treating soln., parts by wt.

Irradia- Acid Soaking time, tion dose, Wt. gain gr./10 temperature, C. mrad. percent gm.

38Q 38R (control).

. 2OAA,80 H;0 20 AA, so 1120 20 16 hrs, 25, 20 min., 90 30 min., 90.

Wt loss... N D.

r N.D N.D.

min.,90 l 1 4.0 N.D. 60min.,90 None N.D N.D.

1 AA means acrylic acid.

2 DMF means dlmethyl formamide. 3 ND means these values were not determined. 4 SSS indicates a purified sodium styrene su l fonate.

parts maleic anhydride, parts of methoxydecaethyleneoxy methacrylate monomer and 100 parts water. It is irradiated to a total dosage of 20 Mrad using the Van de Graaff electron accelerator, as described hereinabove. The fabric is then subjected to 15 standard washings, followed by rinsing in hard (calcium ion containing) tap water. It is observed to have a Samples 38K and 38L are knitted fabrics from filaments of 70 the polyoxymethylene described and claimed by R. N. Mac

Donald in U.S. Pat. No. 2,768,994.

Following the indicated soaking treatment, the samples are irradiated with 2 Mev electrons at the soaking temperature, using the indicated dose. Suitable controls are similarly much dryer hand than an irradiated comparative control treated, but are not exposed to irradiation. Following the ir- 

2. The composition of claim 1, wherein said polymeric carbonamide substrate is the resinous condensation product of hexamethylene diamine and adipic acid.
 3. The composition of claim 1, wherein said polymeric carbonamide substrate is the resinous self-condensation product of epsilon caprolactam.
 4. A filamentary shaped article comprised of the composition set forth in claim
 1. 5. The composition of claim 1 wherein X is methoxy.
 6. A substrate of a fiber-forming synthetic condensation polymer from the class consisting of (1) a polymeric carbonamide which contains recurring carbonamide groups as an integral part of the main polymer chain separated by at least 2 carbon atoms and (2) polyethylene terephthalate, bearing a chemically bonded coating of which a major proportion is a polyether from the class consisting of (A) methoxypolyethyleneoxy methacrylate and polymers thereof, (B) a polyoxyalkylene glycol, and (C) ethoxyethyleneoxyacrylate, the said coating being grafted to the said substrate via carbon-carbon bonds.
 7. In the process for producing graft polymers, the improvement which comprises continuously passing shaped polymer through an irradiation zone, continuously subjecting said polymer to ionizing irradiation in said zone, while in surface contact with at least one vinyl compound of the group consisting of vinyl and divinyl monomers, said polymer being constituted of a monomer different from the group member used, said irradiation being with an effective radiation dosage to cause graft polymerization of said monomer onto said polymer.
 8. The improvement according to claim 7, in which said polymer is passed through said zone while carrying on at least a portion of its surface, a surface layer of said group member.
 9. The process of claim 7, further comprising the preliminary step of coating the surface of said shaped polymer with said vinyl compound to achieve said surface contact.
 10. In the process for producing graft co-polymers, the improvement which comprises subjecting to high energy (ionizing) radiation a polymer, surface coated with at least one vinyl compound of the group consisting of vinyl and divinyl monomers, and said polymer being constituted of a monomer different from the group member used, said irradiation being with an effective radiation dosage to cause graft polymerization of said monomer onto said polymer.
 11. The process of claim 10, further comprising the preliminary step of coating the surface of said polymer with said vinyl compound and wherein said polymer is a shaped article.
 12. In the process for producing graft copolymers, the improvement which comprises coating the surface of a shaped polymer with a vinyl compound of the group consisting of vinyl and divinyl monomers and then subjecting said shaped polymer to high energy (ionizing) radiation, said polymer being constituted of a monomer different from the vinyl group member used, said irradiation being with an effective radiation dosage to cause graft polymerization of said monomer to said polymer. 